Dyestuff of the anthraquinoneacridone series and process of preparing the same



Patented Aug. 7, 1934 DYESTUFF OF THE 'ANTnRAQUnvoNE ACRIDONE SERIES 'AND PROCESS PREPARING THE SAME OFT:

William Dettwyler, Milwaukee, and Ivan Gubelmann, South -Milwaukee, Wis., assignors, 'by mesne assignments, to E. I. du Pont de Nemours g t & Company, a oorporation of Delaware No Drawing. Application August 13,1931, I

Serial No; 556,936 J- V 11 Claims. (o1. 2605-37) This invention relates to novel dyestufis of the anthraquinone-acridone series. It is an object of this invention to produce novel brown vat dyestuffs possessing valuable dyeing characteristics. Other and further objects of this invention will become apparent as the description proceeds. 1 I In copending application Serial No. 556,938, filed of even date herewith, we have described a series of novel anthrimide-acridone compound of the general formula:

, l wherein R. stands for a radical of the anthraquinone series which may be further substituted by imino-radicals, while (0:) indicates that the group Rr-NH- occupies one of the positions 5 and 8 in the acridonyl-anthraquinone nucleus, the positions of the heterocyclic ring being designated as l, 2. These novelanthrimide-acridone compounds may be prepared by several methods, one of which consists of condensing in the presence of a'copper salt and an inorganic base 5- or 8-amino-1,2-anthraquinone-acridone and a halogen anthraquinone body, for instance, aor B-chloro-anthraquinone, 1,5-dichloro-anthraquinone, l-chloro-5-benzoylamino-anthraquinone, and the like.

We have now found that these novel anthrimide-acridone compounds, although valuable dyestuffs in themselves, may be further condensed to give vat'dyestufis of difierent color and qualities. More particularly, we found that when said anthrimide-acridone compounds are heated with metal halides condensing agents such as aluminum chloride, zinc chloride, ferric chloride and the like, the said compounds are converted into novel and very valuable, dyestulfs of generally brown shades. In this reaction evidently a'ring is formed about and involving the imide (NH) group; however, it is not conclusive whether the product is an acridine or a carbazole compound. In analogous reactions in the art involving the heating of an anthrimide with a metallic chloride, the authorities seem to disagree sharply as to the nature of theiring formed. Some believe that the ring is ofan acridine nature, involving the N atom from the imide group, and the adjacent meso C atom of one of the anthraquinone nuclei. Other authorities,'however, insist that the ring is of a carbazole nature involving the N atom of the imide group, and the two adjacent beta C atoms of the-anthraquinone nuclei. In view .of this uncertainty as to the precise nature of the .ring formed, we shall hereinafter refer to our condensation products merely as ring-closed condensation products of the respective'anthrimides.

Without limiting our invention to any particular procedure, the following examples are given to illustrate our preferred mode of operation. Parts given are parts by weight.

Example 1 parts of common salt (NaCl) and 40 parts of aluminum chloride (anhydrous) are melted together at 140 C. and intothis melt are introduced 10 parts 8-a-anthraquinonylamin0-1,2-anthraquinone-benzacridone. (Example 1 of copending application Serial No. 556,938. The formula of the initial material is most probably and'it may beprepared'by reacting 8-amino-1,2- anthraquinone=benzacridone with a-chlormanthraquinonel The melt is stirred at about 140 to 145 C; forl hour, 'then poured into 1000 parts of hot Water, boiled and filtered. The filter cake is washed with hot Water until freeof inorganic salts, dried and ground. I t

The productis a brownish-black powder; insoluble in water dilute acids, or dilute alkalis. It is sparingly soluble inhot nitrobenzene with a cherry red coloration.- It dissolves readily inconcentrated sulfuric acid with a red brown color, but precipitates therefrom on dilution with water in the form of brown flocks. If the dilution is regulated carefully until the concentration of sulfuric acid in themass is about 78%, the dyestuff precipitatesin the form of needle-like crystals which may be filtered off. This procedure may be used to effect purification of the dyestufi.

The b v msmqtl eadil sa a e in usual a ka ine. yi t fi at w th ada k r vt to blackbolor'fron i'which cotton is dyed yellowish brown to brown shades of excellent fast ness qualities. 7

If the above product is chlorinated in the usual manner, for instance by meansjjoi chlorine gas;

in nitrobenzene suspension; itssoliubility in th hydrosulfite vat is decreased.

Example 2 100 parts of zinc chloride are fused at a tern; perature of about 230 C., the fuio'n"atldw "tem'-' perature being facilitated bythe addition ofi water. 10 parts of 8-u-anthraquinonylaniino=1,2 ,7 anthraquinone-benzacridone are now introduced The melt is stirred at 220-230 C. for 1 hour, and'' Eeme si t The procedure isthe sameas in Example. 1, except that in 'lieu' of the anthrir'nide. therein. men tioned, "herein' 10 parts of '5-.u-anth.raquinonyl amino=1 ,2anthraquinone benzacrildonet are used. (Example 2: of" ic'opending application Sen. No. 556,938. The formula; OfTthiSWCOmDDUQdAiSmOSt probably:

and it may he obtained byreacting 5-amino-1,2- anthraquinone-benzaci"idorie with oz-ChlOI'O-QII- thraquinone.')"'" V The product is a brownish-black powder; insoluble in waterjdil ute acids, or dilute alkalis. It is sparingly soluble iii;hot"nitrobenzene with a red coloration. It dissolves readily in concentratfi t purification oil-the dxe if Theirabove product is readily? soluble in the usual-alkaline. hydrosulfiteyat ,witha dark:b1; Qw1 1 to black color froni-whichvcottonlis.dyed; in brown shades? of excellent fastnesslqualities. j

duced 10 parts of 1,5-bis (LQ-benZacridonyl-S- anthraquinonylamino)-anthraquinone. (Example 3 "of oopending application sen. No. 556,938. "il fiwmlw mman i most ro y:

and .itemay be prepare by ...r. aeting; 2- molester aeaminoe1,2-anthtaquinone:benzacridoue,with 1 oletofi;1-,5;-dichloro-anthraquinone. h melt-is stirred. atabeut r 14.0, to.v lefifi. fox-4 abo t. 1 hour, and the reaction product isolated: asi'naExample l.

The product has in general properties similar to that of Example 1, except that it dyes cotton in red-brown'gshades.

Example 5 The proofidure is the same as in Example 1, except that in lieu of the anthrimide body therein mentioned, herein ,10 pa jl s of 8-fi-anthraquinonylamino- 1,2 arithraquinone-benzacridone are used. (Example 4 of copending application Ser. No. 38 he ormu a. o this z qmnqund is mostpmbably; n

m x he; menarea h lneeet nefi-amina1 2- anthraquinone-benzaQr deue; ith; fi-chlQrQl-am thraquinoneh I Thefproduct is a black-powder;insoluble in water, diluteac'ids .ortdilutealkalisl It.is..some,-. what solub-le inhot nitrobenzenewith a. r'edcolora ation.' It dissolves readily; iri concentratedsuh wah a'redprown'6010;, but precipitates lutiOn'jy'ith Water in the'lforr n steadily} biubi; i ftihe usual wane brown 5 1 331: olor; from .n.,, 1r.9w shade -1 Example 61:

'line rerze mzelis he sam asin fi am lell xcept.;.that .$;im.. -h ge ltl -q (5L-benzoylamin li-antm: ampny i 2eanthraquinoneebenzaoltidpnel .a c eaussclishades.

1,969,216 3 amp 5 of p nd r 'appl cation Ser. No, 556,938; 2. The rocessor producing yatd estuffs which The formula of this compound is most probably: comprises heating with a t n mih agent an anthrimide-acridone body of the fol- Ooo-NH c lowing'generalformula: I 4

and it may be prepared by reacting together 8- amino- 1,2 anthraquinone-benzacridone with 1- chloro-5-benzoylamino-anthraquinone. wherein R stands for a hydrogen atom, an aroyl- The product is a dark-brown to black powder; imino group of the benzene series, or a radical of insoluble in water, dilute acids or dilute alkalis. the type It is somewhat soluble in hot nitrobenzene with a cherry red color. It dissolves readily in concentrated sulfuric acid with a brownish-red color,

but precipitates therefrom upon dilution with wa ter in the form of dark-brown flocks. It is readily soluble in the usual hydrosulfite vat with a brownish color, from which cotton is dyed in brown It will be understood that many variations and modifications are possible in our preferred procedure, without departing from the spirit of this invention.

In the above disclosure it should be understood that Wherever we are referrmg to the dyemg and wherein (a) indicates that the NH group is of cotton, we imply, of course, the usual procedure attached to one of therpositions 5 and 8. of with jf %gg g 3; The process of 'producii1'g vat 'dyestufis' an aera 1on or 0x1 a ono e ye ma ena. 1 1 a V7 In the claims below it should be understood that g g gggggi g fil i f gg z gggf i gggii where new products, dyestufis, or articles of mani s e 3 ufacture are claimed, we mean to include these h 9 19W e5gFe q i ia bodies not only in substance, but also in whatever state they exist when applied to material dyed,

printed, or pigmented therewith.

We claim: 7 1 '1. The process of producing vat dyestuffs which comprises heating with a metal halide condensing agent ananthrimide-acridone body of the following general formula:

(III, HN Q 7 s 1 o f R NH wherein (0:) indicates that ,the NH group is 5 attached toone of the positions 5 and 8. v 1

g 4. The process of producing; vat dyestuffs 0 wherein R stands for a radical of the anthraquinwhich comprises heating with. metal" halide one series, while (0:) indicates that the NH group condensing agent an anthrimide-acridone y is attached to one of the positions 5 and 8. 0f t following general formula:

whereinpfiuh indicatesihat ttheaN H-t group is attached-fitotonelofi the positions 5 and 8.

5. vThe 'process'eof'produoing. Matldyestufis which comprises heating with Ta metal Ihalide' coli- '5, densing agent an anthriiriide -acridohe"b6d37"6f the following general formula:

wherein (a) indicates that the NH group is attached to one of the positions 5 and 8. 6. Ring-closed condensationrproducts of anthrimide-aeridonesrof the following general formula:

' I 1' 1 i whereini'R stands for I aradical of the anthraqui'nonepeseries whiley (a) .indieates that the NH 40 group. is-attached? :tQ-one; of the positionsfi and 8; said products beinguinesolidnforni generally dark powders, insoluk'ili'n water, dilute acids,'o'r dilute alkalis; readily soluble in concentrated sulfuric acid with reddish-brown colors, but pre- 7 cipitating, therefrom upon dilution with water in the form of brown flocks; said products being soluble in 1111811181131 alkaline hydrosulfite vat with brown to black colors, from whichzicotton may 7 h be dyed' in -the usuakn'ranner in'brownshades.

'7. Ring-closed condensation zproduct's of anthrimideacridones of the :follwing general formula:

wherein R stands for a hydrogen atom, an aroylimino group of the benzene series, or a radical of the type 6' j to alkaline hydrosulfite Vat w'i tlr ear and wherein 6:) indicates that the group is attached -to one of-th,e --positi-'ons-5 and- 8; said products being in solid form generally dark powders, insoluble in water, dilute acids, or dilute alkalis; readily ommem concentrated sul-ifuric acid with reddish brown colors, but pre- .8 ie s unse e e aiith" *fiid aerid'one' of the following 1 general formula:

156 black color'f-rom which cotton may be dyed in the usual mariner in brown shades.

9. A rizig-closed condensation product of an anthrimide' acridone of the following general formula:

wherein (a) indicates that the NH group is attached to one of the positions 5 and 8; said product being in solid form a brownish-black powder;

insoluble in water, dilute acids, or dilute alkalis;

readily soluble in concentrated sulfuric acid with a red brown color, but precipitating therefrom upon dilution with water in the form of brown flocks; said product being soluble in the usual alkaline hydrosulfite vat with a dark-brown to black color from which cotton may be dyed in the usual manner in red-brown shades.

10. The process of producing vat dyestuffs which comprises heating with a metal halide condensing agent an anthrimide-acridone body of the following general formula:

HN l O 2 (a) RNH- H 0 wherein R stands for a radical of the anthraquinone series which may be further substituted by an aroyl-imino group of the benzene series or by a benzacridone ring, while (0:) indicates that the NH group shown is attached to one of the positions 5 and 8.

l1. Ring-closed condensation products of anthrimide-acridones of the following general formula:

EN 0 /8\ & O @R-NH-t/ 5 a wherein R stands for a radical of the anthraquinone series which may be further substituted by an aroyl-imino group of the benzene series or by a benzacridone ring, while (a) indicates that the NH group shown is attached to one of the positions 5 and 8; said products being in solid form generally dark powders, insoluble in water, dilute acids, or dilute alkalis; readily soluble in concentrated sulfuric acid with reddish-brown colors, but precipitating therefrom upon dilution with water in the form of brown flocks; said products being soluble in the usual alkaline hydrosulfite vat with brown to black colors, from which cotton may be dyed in the usual manner in brown shades.

WILLIAM DE'ITWYLER. IVAN GUBELMANN. 

